EP2625729B1 - Elektromechanische wirkung bei metalloxiden - Google Patents

Elektromechanische wirkung bei metalloxiden Download PDF

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Publication number
EP2625729B1
EP2625729B1 EP11788584.8A EP11788584A EP2625729B1 EP 2625729 B1 EP2625729 B1 EP 2625729B1 EP 11788584 A EP11788584 A EP 11788584A EP 2625729 B1 EP2625729 B1 EP 2625729B1
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EP
European Patent Office
Prior art keywords
active material
stress
electromechanical
electric field
ranges
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EP11788584.8A
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English (en)
French (fr)
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EP2625729A2 (de
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Igor Lubomirsky
Roman Korobko
Anna Kossoy
Harry L. Tuller
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Yeda Research and Development Co Ltd
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Yeda Research and Development Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
    • H10N30/204—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators using bending displacement, e.g. unimorph, bimorph or multimorph cantilever or membrane benders
    • H10N30/2041—Beam type
    • H10N30/2042—Cantilevers, i.e. having one fixed end
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/076—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by vapour phase deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/42—Piezoelectric device making

Definitions

  • This invention provides an electromechanical device comprising an active material comprising a metal oxide such as Ce 0.8 Gd 0.2 O 1.9 wherein the elastic modulus of metal oxide can be modulated by applying external electric field.
  • the Ce 0.8 Gd 0 . 2 O 1.9 layer in a substrate ⁇ electrode ⁇ Ce 0.8 Gd 0.2 O 1.9 ⁇ electrode structure or conductive substrate ⁇ Ce 0.8 Gd 0.2 O 1.9 ⁇ electrode structure develops a stress upon applying an electric field.
  • This invention provides methods for tailoring the elastic modulus of materials using an electric field for the generation of an electromechanical response.
  • Electromechanically active materials i.e., materials developing mechanical stress in response to the application of an external electric field are of a great importance for a wide range of applications ranging from electromechanical transducers to micro-pumps.
  • piezoelectric and electrostrictive There are two major classes of materials currently in use: piezoelectric and electrostrictive.
  • Classical piezoelectric and electrostrictive materials have electromechanical response well below 1 nm/V, typically 0.2-0.3 nm/V. This implies that generation of a 1 ⁇ m displacement requires application of a few thousand volts of external bias. No noticeable improvement in performance has been achieved during the last three decades.
  • both piezoelectric and electrostrictive materials may develop stress of hundreds of MPa, small displacements restrict their field of applications.
  • Thin films of Ce 0.8 Gd 0.2 O 1.9 one of the most important ionic conductors, exhibit a number of elastic anomalies, i.e. both spontaneous changes in lattice parameter as well as inelastic effects. The most striking of these is the ability to exhibit two different elastic moduli depending on time scale. This phenomenon, which has been called the chemical strain effect, can cause an absolute change in volume of ⁇ 0.2% even if the external stress is homogenous. As such, the internal reorganization of point defects has been cited as a probable cause of the inelastic behavior (chemical strain) rather than the more commonly observed stress gradient-induced diffusion.
  • Heating decreases the repulsion between the Ce 4+ ions and the oxygen vacancies, thereby restoring the more symmetrical environment and leading to film flattening.
  • the activation energy deduced from the film flattening time is comparable to that measured for the self-supported Ce 0.8 Gd 0.2 O 1.9 films. This suggests that the microscopic processes jointly responsible for local distortions and elastic anomalies are similar for both oxygen deficient and Gd-doped ceria.
  • Ce Ce -V O cerium-oxygen vacancy
  • the analysis discussed herein above indicates that the cerium-oxygen vacancy, Ce Ce -V O , interaction forms an elastic dipole, which can easily reorient under external stress similar to Gorky or Snoek effects.
  • the Gorsky and Snoek effects are usually observed in electrically conductive materials (metals or alloys).
  • the uniqueness of the Ce Ce -V O elastic dipole is that at room temperature, Ce 0.8 Gd 0.2 O 1 . 9 is a poorly conductive material. Therefore, Ce Ce -V O dipoles may reorient under an external electric field. The reorientation takes place by moving of the oxygen vacancy to the neighboring oxygen site. Since, Ce 0.8 Gd 0.2 O 1 .
  • the present invention provides an electromechanical device, actuator or sensor comprising a ceria-based material, wherein upon application of an electric field said ceria-based material generates displacement, stress or a combination thereof, according to the independent claims 1, 2, and 6. Further advantageous features are covered by the dependent claims.
  • this invention provides an electromechanical device comprising an active material wherein upon application of an electric field the active material generates large displacement, large stress or a combination thereof.
  • the active material is a ceria based material.
  • the active material is Ce x Gd y O z wherein x ranges between 0.95-0.63, y ranges between 0.05-0.37 and z ranges between 2-(y/2).
  • the active material comprising Ce 0.8 Gd 0.2 O 1.9
  • the active material is Ce 0.8 Gd 0.2 O 1.9 .
  • the active material develops stress upon application of the electric field.
  • electromechanical devices of this invention find use in any application in which piezoelectric materials or electrostrictive materials are currently used. In one embodiment, devices of this invention are applicable to any sensor and to any actuator that requires an electromechanical material.
  • electromechanical devices of this invention comprise active materials that can develop much larger stress and/or exhibit much larger displacement or deformation upon application of an electric field as compared with conventional piezoelectric or electrostrictive materials.
  • a certain degree of strain is required for the electric field-induced development of stress and/or for the electric-field induced displacement or deformation in active materials of this invention.
  • the active material is strain-free for the electric field-induced development of stress and/or for the electric-field induced displacement or deformation in active materials of this invention.
  • strain in the active material can be generated by production of the material from its components by chemical or physical methods such as chemical reactions, precipitation from solutions, re-melting, phase separation and etc.
  • strain in the active material can be generated by production or forming of the device or the active material from unstrained/non-active material by chemical or physical or material engineering methods such as: evaporation, CVD, PVD, depositions from gel or solutions, powder metallurgy techniques, deposition from liquid or gas phases, sintering and any other method known to a person of ordinary skill in the arts.
  • strain in the active material can be generated by inducing strain into unstrained/non-active material to make active material using heat treatments such as annealing, tempering, quenching and similar processes.
  • strain in the active material can be generated by inducing strain into unstrained/non-active material to make active material by mechanical methods such as pulling, bending, compressing, twisting etc.
  • the elastic modulus of Ce 0.8 Gd 0.2 O 1 . 9 can be modulated by applying an external electric field.
  • the electric field is constant (DC).
  • the electric field is alternating (AC).
  • the electric field is a combination of AC and DC.
  • the active material layer in a substrate ⁇ electrode ⁇ Ce 0.8 Gd 0.2 O 1.9 ⁇ electrode structure develops a stress of 0.5 GPa under applied electrical field of 150 kV/cm.
  • the active material layer in a substrate ⁇ electrode ⁇ Ce 0.8 Gd 0.2 O 1.9 ⁇ electrode structure develops stresses ranging between 0.1-1 GPa under applied electrical fields of 5-200 kV/cm.
  • the active material layer in a substrate ⁇ electrode ⁇ Ce 0.8 Gd 0.2 O 1.9 ⁇ electrode structure develops a stress according to Example 2 and Figures 8, 9 and 10 .
  • the electromechanical response is observed in films of this invention with initial in-plane strain of 0.1% ⁇ u ⁇ 0.4% having a characteristic response time from a few hours to a few minutes. In one embodiment, the electromechanical response is observed in films of this invention with initial in-plane strain of 0.1% ⁇ u ⁇ 0.6%. In another embodiment, the electromechanical response is observed in stain-free films of this invention.
  • the response time may comprise the "forming step” (like poling in piezoelectrics), which can take 1-10 hours, and further comprise "fast response” after forming, which can be 1sec - 15 min.
  • the observed electromechanical response originates in the change in the elastic modulus rather than in long range diffusion.
  • change in elastic modulus means change in the interatomic forces and can be achieved by small movement, shift or reorientation of atoms, without involving translation of matter or diffusion.
  • tailoring of elastic modulus of the active material by the electric-field induced rearrangement of point defects generates an electromechanical response.
  • the active material of this invention which are ionic conductors possess elastic dipoles because they contain concentrations of point defects that are comparable with the concentration of ions in the lattice (for instance in Ce 0.8 Gd 0.2 O 1.9 5% of oxygen sites are empty).
  • most ionic conductors contain aliovalent or homovalent dopants that cause local lattice distortions.
  • "alio” means different
  • "homo” means the same, i.e. dopants with valence different or equal to the host.
  • Homovalent dopants may cause local lattice distortions due to size difference.
  • the high mobility of ions and low electronic conductivity in these materials imply that the elastic dipoles may rearrange under an external field.
  • modification of elastic properties of the active materials of this invention by an external field may be observed in non limiting examples such as doped or undoped ZrO 2 , CeO 2 , Bi 2 O 3 , and oxides of Sr, La, Fe, Co in one embodiment.
  • the limitation of piezoelectric and electrostrictive materials is not applicable to the described effect.
  • the stress of Ce 0.8 Gd 0.2 O 1.9 is defined by the changes in the elastic modulus of Ce 0.8 Gd 0.2 O 1.9 , where the displacement is defined only by geometrical factors (lengths of the sample for the scheme in Fig. 2 ). Therefore, the observed effect is a qualitatively different type of electromechanical response.
  • Ce 0.8 Gd 0.2 O 1.9 cannot be piezoelectric or electrostrictor due to its lattice symmetry and low dielectric constant. Therefore, the observed effect is a qualitatively different type of electromechanical response. Meaning that the limitation of piezoelectric and electrostrictive materials (either small displacement or small stress) is not applicable to the described effect, and higher performances can be achieved by devices and methods of this invention.
  • an electromechanical device of this invention is a device that exhibits a mechanical change upon the application of an electric field.
  • an electromechanical device is a mechanical device that is operated by electricity.
  • an electromechanical effect is the effect underlying an electrically operated mechanical device.
  • an electromechanical effect is the effect of electricity (an electric field) on a mechanical property of a material.
  • an electromechanical effect can be described as deformation, as a change in shape, geometry, density, length, width, thickness, bending, curvature, porosity, rigidity, flexibility, stress or a combination thereof as a function of applied electric field on the material.
  • the effect as demonstrated by the material is parallel to the direction of the electric field.
  • the effect is perpendicular to the electric field. In one embodiment, the effect is exhibited both parallel and perpendicular to the electric field. In one embodiment, the effect along one direction (one axis) in the material is different from the effect along another direction in the material. In one embodiment, the effect is better pronounced at the surface of the material. In one embodiment, the effect is a bulk effect. In one embodiment, the electromechanical effect is reversible, i.e. application of electric field creates the effect; turning off the electric field - the effect disappears.
  • an active material is the material responsible for the electromechanical effect. In one embodiment, the active material is the material that undergoes a mechanical change as a response to an applied electric field.
  • displacement is a change in the position of the active material or portions thereof.
  • displacement means change of location, change of the coordinates of the active material or portions thereof.
  • displacement describes the movement of the active materials or portions thereof as a result of an applied electric field.
  • a displacement is observed as change in length, increased or decreased curvature, bending or increase/decrease in bending, elongation, shrinkage, change in volume, change in width, or any other change in the dimensions or in the geometry of the active material or portions thereof.
  • force is exerted by the active material upon application of an electric field.
  • force is developed in the active material.
  • the active material when the active material is under the influence of an electric field, the active material can resist an external force.
  • the active material of this invention generates a mechanical force as presented in Example 3.
  • deformation is a change in dimensions of a material. In one embodiment, deformation is equivalent to or comprising displacement as descried herein above.
  • strain is the amount of deformation a material experiences per unit of original length in response to stress.
  • in-plane strain is the strain within the thin film directed perpendicular to the smallest dimension of the film.
  • the in-plane strain in thin films can be described as follows: in the thin film technology, due to the fact that thin films have one dimension much smaller than two others, most properties can be roughly divided to two classes: in-plane & out-of-plane.
  • the in-plane parameters refer to the parameters directed perpendicular to the "thin" or to the smallest dimension of the thin film.
  • in-plane strain is the strain within the thin film or within the active material.
  • elastic modulus is the ratio of stress, within the proportional limit, to the corresponding strain. In one embodiment, elasticity is the tendency of a material to return to its original shape after it has been stretched or compressed.
  • pm represents units of picometers. In one embodiment, nm represents units of nanometers. In one embodiment, MPa represents units of Mega Pascal. In one embodiment, V represents Volts. In one embodiment, ⁇ m represents micrometers.
  • stress is the force that a material is subjected to per unit of original area. In one embodiment, stress in materials of the invention depends on voltage (bias/electric field) applied.
  • contacts are conducting contacts.
  • the conducting material from which the contacts are made comprising metal.
  • the conductive contacts comprise any other material with metal-like conductivity, such as conductive oxides, highly-doped semiconductors or conductive polymers.
  • a substrate is the supporting structure of the device.
  • the substrate is the material on which or in which the device is built.
  • the substrate is a piece of material from which the device or portions of it will be made.
  • the substrate comprising is pyrex, silicon dioxide, silicon nitride, quartz or SU-8.
  • the substrate comprising glass.
  • the substrate is coated.
  • the substrate, comprising silicon In one embodiment, the substrate, comprising a polymer. In one embodiment, the polymer is PDMS.
  • the substrate width/length/diameter or any other surface dimension equals or is similar in size to the surface dimensions of the active material.
  • the surface of the substrate is larger than the surface of the active material.
  • the substrate is comprised of a transparent material.
  • the substrate is conductive.
  • conductive substrate is a metal, graphite, low-resistance semiconductor, conductive ceramic, conductive polymer/plastic.
  • the substrate is curved when the active material and conductive contacts layers are formed in contact with the substrate according to embodiments of the invention.
  • the radius of curvature of the substrate follows the radius of curvature imposed by the strain/stress in the active material.
  • the curvature of the substrate may change.
  • radio frequency magnetron sputtering is a physical vapor deposition (PVD) method of depositing thin films by sputtering, that is ejecting material from a "target", (a source of material), which then deposits onto a substrate.
  • target composition is the same as the composition of the active material, i.e. Ce 0.8 Gd 0.2 O 1 . 9 in one embodiment.
  • the sputtering process can be performed in vacuum of 0.66-13.3 Pa (5-100 millitorr), in presence of Ar, O 2 , or a mixture of Ar and O 2 .
  • the electrical power of a power supply used for radio frequency sputtering may be 50-300 Watt.
  • an electric field is the space surrounding an electric charge. In one embodiment, the electric field exerts a force on other electrically charged objects. In one embodiment, a stationary charged particle in an electric field experiences a force proportional to its charge. In one embodiment, an electric field can be induced by applying a voltage. In one embodiment, an electric field can be induced in the area between two electrodes to which an unequal voltage is applied. In one embodiment, certain distribution of positive or negative charges in space can give rise to an electric field.
  • devices used in this invention are made by deposition, evaporation or sputtering processes or a combination thereof.
  • further methods used in the preparation of devices of the invention comprise lithography and etching processes, electron beam deposition/evaporation, thermal evaporation, electrochemical deposition, stamping, imprinting, and any other conventional processes used in e.g. the semiconductor fabrication industry as will be known to a person skilled in the art.
  • a sensor is a device that measures a physical quantity and converts it into a signal which can be read by an observer or by an instrument.
  • an actuator is a mechanical device for moving or controlling a mechanism or system, by converting the electrical energy to mechanical energy.
  • an actuator comprising electrical motors, electrical pumps and valves.
  • an actuator actuates electrical motors, electrical pumps and valves.
  • the actuator activates, triggers, sets in motion, puts into action and/or starts a device, a system an apparatus or portions thereof.
  • a power supply is used for the generation of an electric field.
  • connectors or wires from the power supply are connected to the conductive contacts of the active material in devices of the invention.
  • the active material is represented by Ce x Gd y O z .
  • x, y, and z represent the concentrations of each ion in the crystal.
  • the present invention's active material is ceria-based material.
  • the active material is Ce x Gd y O z wherein x ranges between 0.95-0.63, y ranges between 0.05-0.37 and z ranges between (2-(y/2)).
  • z 1.9.
  • x, y and z denote the relative concentrations of each ion in the solid.
  • Active materials of this invention comprise derivatives of CeO 2 .
  • the general formula for such derivatives is Ce X M Y O (2-delta) wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ delta ⁇ 1, and wherein M is any metal that has a valency less than or equal to 4, i.e., any metal that causes vacancy formation or promotes oxygen deficiency if introduced into CeO 2 .
  • M may be any of all lanthanides, Ca, Sr, Fe, Y, Sc, Zr, Ti, Ni, Co or combinations thereof.
  • active materials of the invention may comprise more than one dopant (i.e. M as described herein above) as long as the material preserves local fluorite-like structure. The macroscopic structure is less important as long as the local arrangement is preserved.
  • the piezoelectric coefficient in materials of this invention is about 100 pm/V, in a material with elastic modulus >100 GPa.
  • the substrate of this invention comprising glass. In one embodiment, the substrate comprising a polymer. In one embodiment, the substrate comprising PDMS or teflon.
  • the thickness layer of the active material ranges between 500 nm and 1000 nm. In one embodiment, the thickness layer of the active material is 500 nm. In one embodiment, the thickness layer of the active material ranges between 500 nm and 750 nm. In one embodiment, the thickness layer of the active material ranges between 750 nm and 1000 nm. In one embodiment, the thickness layer of the active material ranges between 100 nm and 1000 nm. In one embodiment, the thickness layer of the active material ranges between 500 nm and 2000 nm. In one embodiment, the thickness layer of the active material ranges between 400 nm and 4000 nm. In one embodiment, the thickness layer of the active material ranges between 600 nm and 800 nm. In one embodiment, the thickness layer of the active material ranges between 1000 nm and 10,000 nm. In one embodiment, the thickness layer of the active material ranges between 10,000 nm and 100,000 nm.
  • the length and width of the active material equal. In one embodiment, the length of the active material is larger than the width of the active material. In one embodiment, the length and the width of the active material are larger than the thickness (height) of the active material. In one embodiment, the length of the active material is four centimeters and the width of the active material is 0.8 cm.
  • the length of the active material, the width of the active material or a combination thereof ranges between 0.5 cm and 5 cm. In one embodiment, the length of the active material, the width of the active material or a combination thereof ranges between 0.1 cm and 1 cm. In one embodiment, the length of the active material, the width of the active material or a combination thereof ranges between 1 cm and 10 cm. In one embodiment, the length of the active material, the width of the active material or a combination thereof ranges between 10 cm and 100 cm. In one embodiment, the length of the active material, the width of the active material or a combination thereof ranges between 0.01 cm and 0.1 cm.
  • the length of the active material, the width of the active material or a combination thereof ranges between 10 micrometer and 100 micrometers. In one embodiment, the length of the active material, the width of the active material or a combination thereof ranges between 1 micrometer and 10 micrometers. In one embodiment, the active material is in the form of a disc. In one embodiment, the diameter of the disc may comprise any value as described herein above for the width/length of square/rectangular active materials. In one embodiment, the thickness of the disc is any value described herein above for the thickness of the active material. In one embodiment, the active material may comprise any geometrical shape, or it can be of an undefined or partially defined geometry. In cases where the geometry of the active material is not well-defined, the values described herein above for length/width and thickness may represent the largest and/or smallest dimensions of the active material.
  • the density of the active material ranges between 7.2 - 7.7 g/cm 3 .
  • the dielectric constant of the active material ranges between 20-28.
  • the Young's modulus of the active material ranges between 200-250 GPa.
  • the contacts of this invention are made of a conducting (conductive) material.
  • a contact is an electrode.
  • the first layer deposited on the substrate is a contact or an electrode.
  • the contacts comprising metal.
  • the metal is Cr.
  • the metal comprising Al, Cr, Mo, Ag, Au, Ti or a combination thereof.
  • any metal can be used to form the conductive contacts.
  • the contacts comprising a metal alloy.
  • any other material with metal-like conductivity, such as conductive oxide, highly-doped semiconductor or a conductive polymer may be used for the contacts in embodiments of this invention.
  • the contact is a metal, graphite, low-resistance semiconductor, conductive ceramic, conductive, polymer/plastic or combination thereof.
  • the substrate is conductive, there is no need for the first electrode and the active material is deposited directly on the conductive substrate.
  • a conductive substrate is also a contact.
  • the thickness of at least one contact is 100 nm. In one embodiment, the thickness of at least one contact ranges between 50 nm and 150 nm. In one embodiment, the thickness of at least one contact is 500 nm. In one embodiment, the thickness of at least one contact ranges between 30 nm and 300 nm. In one embodiment, the thickness of at least one contact is 1000 nm. In one embodiment, the thickness of at least one contact ranges between In one embodiment, the thickness of at least one contact is 100 nm. In one embodiment, the thickness of at least one contact ranges between 100 nm and 500 nm. In one embodiment, the thickness of at least one contact is 200 nm.
  • the thickness of at least one contact ranges between 70 nm and 130 nm. In one embodiment, the thickness of at least one contact is 20 nm. In one embodiment, the thickness of at least one contact ranges between 50 nm and 1000 nm. In one embodiment, the thickness of at least one contact is the minimum thickness of a certain metal (or other conductive material) that will provide a good electrical contact. In one embodiment, the thickness of the two contacts is the same. In one embodiment, the thickness of each contact is different.
  • the contacts cover the full surface of the active material. In one embodiment, the contacts cover only portions of the active material surface. In one embodiment, the two contacts comprising the same material. In one embodiment, each of the two contacts comprising a different material.
  • materials of the invention are centrosymmetric with a low dielectric constant. In one embodiment, materials of the invention can not be defined as classical piezoelectrics and can not be defined as classical electrostrictive materials.
  • the active material can display the electromechanical properties as a thin film. In one embodiment, the active material can display the electromechanical properties as a bulk material. In one embodiment, because the active material is evaporated (sputtered) on a different material, the active material will be strained. In one embodiment, bending of the active material, bending and fixing the bent active material to another material or to a holder, stretching the active material and fixing it to another material, all such actions may generate in-plane strain in the active material.
  • active materials of this invention generate both large force and large displacement upon application of an electric field.
  • stress and displacement in active materials of the invention in response to electric field are ten times higher than stress and force generated by conventional electromechanical materials.
  • the stress developed in active materials of this invention ranges between 100 MPa and 500 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 1 MPa and 100 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 1 MPa and 10 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 100 MPa and 1000 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 500 MPa and 2000 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 50 MPa and 1000 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 100 MPa and 5000 MPa. In one embodiment, the stress developed in active materials of this invention ranges between 500 MPa and 1500 MPa. In one embodiment, the stress developed in active materials of this invention depends on the applied electric field.
  • displacement in active materials of this invention ranges between 50 pm/V and 150pm/V. In one embodiment, displacement in active materials of this invention ranges between 10 pm/V and 150 pm/V. In one embodiment, displacement in active materials of this invention ranges between 10 pm/V and 50pm/V In one embodiment, displacement in active materials of this invention ranges between 100 pm/V and 1000pm/V. In one embodiment, displacement in active materials of this invention ranges between 100 pm/V and 500pm/V. In one embodiment, displacement in active materials of this invention ranges between 100 pm/V and 1500pm/V. In one embodiment, displacement in active materials of this invention ranges between 50 pm/V and 300pm/V. In one embodiment, displacement in active materials of this invention ranges between 500 pm/V and 1000pm/V. In one embodiment, the displacement in active materials of this invention depends on the applied electric field.
  • active materials of this invention generate both large stress and large displacement (or deformation). According to this aspect and in one embodiment, combination of any range described herein above for stress values and any range described herein above for displacement values can describe values of displacement and stress in active materials of the invention.
  • the electromechamical effect dependent on the internal strain in one embodiment, the electromechamical effect dependent on the internal strain. In another embodiment, the electrochemical effect is provided in strain-free samples of this invention.
  • the electromechamical effect is influenced by electron conductivity of the ceria-based material or by the impedance of the experimental setup and/or test structures.
  • the conductive contacts are connected to a power supply.
  • voltage is applied by the power supply to the device in order to generate the electric field.
  • the voltage is referred to as "bias".
  • the electric field is constant (DC).
  • the electric field is alternating (AC).
  • the electric field is a combination of AC and DC.
  • the voltage that is applied to the device is ⁇ 2V. In one embodiment, the voltage that is applied to the device ranges between 0V and ⁇ 4V. In one embodiment, the voltage that is applied to the device ranges between 1V and ⁇ 4V. In one embodiment, the voltage that is applied to the device ranges between 1V and ⁇ 5V. In one embodiment, the voltage that is applied to the device ranges between 0.01V and ⁇ 10V. In one embodiment, any voltage or voltage range that will generate the electromechanical effect in devices of this invention may be applied to devices of this invention. In one embodiment, voltage may be applied continuously. In one embodiment, voltage application can be pulsed. In one embodiment voltage can be direct voltage and in another embodiment, voltage may be alternating voltage.
  • the voltage applied may be switched on and off. In one embodiment, switching the voltage ON and OFF at constant time intervals and in another embodiment, in different time intervals. In one embodiment, the voltage applied is constant. In one embodiment, the voltage applied is not constant. In one embodiment, the voltage applied is gradually increased or gradually decreased.
  • the active material is curved with a positive curvature
  • application of an electric field may change the curvature of the material such that it will become a negative curvature and vice versa.
  • the radius of curvature of the active material (and/or the radius of the support/substrate/contacts) will change upon application of an electric field, but the direction (sign) of the curvature will remain the same.
  • this invention provides an electromechanical device comprising an active material wherein upon application of an electric field said active material generates displacement, stress or a combination thereof.
  • this invention provides an electromechanical device comprising an active material wherein upon application of an electric field said active material generates large displacement, large stress or a combination thereof.
  • this invention provides an electromechanical device comprising a ceria-based material wherein upon application of an electric field said active material generates large displacement, large stress or a combination thereof.
  • the in-plane strain of the active material ranges between 0.1%-0.4%. In another embodiment.
  • the active material is strain free.
  • the active material comprises Ce x Gd y O z as set out above. In one embodiment, the Ce x Gd y O z is Ce 0.8 Gd 0.2 O 1.9 .
  • x ranges between 0.95-0.63
  • y ranges between 0.05-0.37
  • z ranges between 2-(y/2).
  • the displacement is at least 100 pm/V.
  • the stress developed in the active material upon application of the electric field is at least 100 MPa.
  • the device further comprises conductive contacts.
  • the contacts comprise metal.
  • the metal contacts comprise Cr, Al, Ag, Ti or combination thereof.
  • the thickness of the metal contacts ranges between 50 nm and 150 nm.
  • the device is supported by a substrate. In another embodiment, if the substrate is conductive, it is used as a contact.
  • the substrate comprises glass. In one embodiment, the thickness of the glass ranges between 50 micrometers and 500 micrometers.
  • the active material layer is formed by radio frequency magnetron sputtering. In one embodiment, the thickness of the active material layer ranges between 0.35 and 1.0 micrometers.
  • this invention provides a sensor comprising a device, wherein the device is an electromechanical device comprising an active material of this invention wherein upon application of an electric field the active material of this invention generates displacement, stress or a combination thereof.
  • this invention provides an actuator comprising a device, wherein the device is an electromechanical device comprising an active material of thios invention wherein upon application of an electric field the active material of this invention generates displacement, stress or a combination thereof.
  • the electromechanical effect in devices of this invention reflects the electromechanical interaction between the mechanical and the electrical states in the active material. In one embodiment, the electromechanical effect in devices of the invention is reversible. In one embodiment, devices of this invention exhibit the effect of internal generation of a mechanical force resulting from an applied electrical field.
  • the active material will deform when an external electric field is applied to the active material.
  • electromechanical devices of this invention find use in applications such as frequency standards, pressure wave generators in air and in water e.g. sound generators.
  • this invention provides an electric field sensor.
  • this invention provides an actuator such as in translation stages, motors, artificial muscles and all other actuator systems wherein conventional piezoelectrics and electrostrictors are currently used.
  • the device when the dimensions of the device or portions thereof are in the micrometer and/or nanometer range, the device may find use in microelectromechanical (MEM) devices such as MEM sensors and actuators.
  • MEM microelectromechanical
  • devices of this invention may find use in electronics, optoelectronics, as components in the semiconductor industry, in micro- and nano-technology.
  • devices of the invention may be used in medical devices.
  • devices of the invention may find use in biotechnology.
  • devices of this invention may be applied to controlled drug release.
  • application of electric field will cause displacement in devices of the invention such that portions of the device will push, pull, trigger or start a mechanical component.
  • such mechanical component is stationary.
  • the mechanical component is in motion.
  • the interaction of the component with devices of the invention puts the component into motion, or in another embodiment, devices of the invention restrict or stop movement of mechanical components.
  • if radiation is reflected from devices of the invention then upon application of an electric field, the direction or axis of reflected radiation changes. In one embodiment, such change may be utilized in opto-electronic devices or in sensors wherein sensing of the change in electric field may be translated to change in radiation received at a local point in space.
  • the device of this invention comprises a ceria-based material of providing comparable electromechanical effect with high-end commercial electromechanically active materials (Examples 1 and 7). With higher operational fields, better elastic properties, absence of depoling and simple manufacturing.
  • the present disclosure also provides a process for making an electromechanical device, the process comprising:
  • the first conductive layer is formed on a substrate.
  • the first step of "forming s first conductive layer" absent and the active material layer is deposited directly on the conductive substrate.
  • the conductive layer is formed by electron beam deposition.
  • the layer of an active material is formed by radio frequency magnetron sputtering.
  • the first and the second conductive layers are connected to a power supply.
  • the in-plane strain of the active material ranges between 0.1%-0.4%.
  • the active material comprises Ce x Gd y O z as set out above.
  • the Ce x Gd y O z comprising Ce 0.8 Gd 0.2 O 1 . 9 .
  • x ranges between 0.95-0.63
  • y ranges between 0.05-0.37
  • z ranges between 2-(y/2).
  • the displacement is at least 100 pm/V. In one embodiment, stress developed in said active material is at least 100 MPa.
  • the conductive layer comprises metal.
  • the metal comprises Cr, Al, Ag, Ti.
  • the thickness of the conductive layer ranges between 50 nm and 150 nm.
  • the device is supported by a substrate.
  • the thickness of the substrate ranges between 50 micrometers and 500 micrometers.
  • the substrate comprises glass.
  • the active material is formed by radio frequency magnetron sputtering. In one embodiment, the thickness of the active material ranges between 0.35 and 1.0 micrometers.
  • the electromechanical device functions as a sensor. In one embodiment, the electromechanical device functions as an actuator.
  • devices can be prepared by any other technique suitable for deposition of Ce 0.8 Gd 0.2 O 1.9 , or for any other active material of this invention e.g. PVD-physical vapor deposition, cathodic arc deposition, electron beam physical vapor deposition, pulsed laser deposition, atomic laser deposition; CVD - chemical vapor deposition: reactive sputtering, microwave plasma-assisted CVD, plasma-enhanced CVD, atomic layer CVD, combustion chemical vapor deposition, metal-organic chemical vapor deposition, hybrid physical-chemical vapor deposition, rapid thermal CVD, vapor phase epitaxy, powder metallurgy techniques, chemical solution deposition and any other technique as described in the art.
  • PVD-physical vapor deposition cathodic arc deposition, electron beam physical vapor deposition, pulsed laser deposition, atomic laser deposition
  • CVD - chemical vapor deposition reactive sputtering, microwave plasma-assisted CVD, plasma-enhanced CVD, atomic
  • electromechanical devices of the invention are used as sensors of electric fields. In one embodiment, electromechanical devices of the invention are used to calibrate, operate, start, generate energy, to sense, to activate, to actuate, to generate movement in, to stop movement of, to push, pull, reflect radiation and/or to measure any device, system, apparatus or portions thereof as would be appreciated by a person skilled in the arts.
  • Ce 0.8 Gd 0.2 O 1.9 was prepared by radio frequency magnetron sputtering: target Ce 0.8 Gd 0.2 O 1.9 , power 100W, pressure in the chamber 4 Pa (30 millitorr), gases Ar, O 2 in ratio of 1:1.
  • the top and the bottom contacts were prepared by electron beam evaporation.
  • the contacts may be of the same metal or of different metals as long as they are chemically stable.
  • Experiments were conducted with Al, Cr, Mo, Ag, Au and Ti.
  • the structures, with lateral dimensions of 8 ⁇ 40 mm, were mounted on a brass stand with one end forming a cantilever ( Fig. 2 ).
  • a voltage of ⁇ (1-4) V was applied between the top and the bottom contacts.
  • Development of stress in the Ce 0.8 Gd 0.2 O 1.9 layer caused bending of the cantilever, which was detected by a home-built curvature measurement setup.
  • a laser beam was sent perpendicular to the sample and the reflected beam was directed to a CCD camera.
  • Table 1 demonstrates typical magnitude of the electromechanical response generated in glass ⁇ metal ⁇ Ce 0.8 Gd 0.2 O 1.9 ⁇ metal structures.
  • CGO denotes Ce 0.8 Gd 0.2 O 1.9 in one embodiment.
  • Table 1 Sample Structure Potential Field ⁇ max pseudo d31 [V] [KV/cm] [Mpa] [pm/V] R7-2 Cr/CGO/Cr 2.5 57 585 490 R7-4 Cr/CGO/Cr 3 68 875 611 R8-1 Al/CGO/Cr 4 77 528 327 R8-2 Al/CGO/Ti 4 77 695 430 R9-6 Cr/CGO/Cr 4 125 459 175 R4-1 Cr/CGO/Cr 2 46.5 1063 1088 Table 2 presents examples of commercial materials with the best known electromechanical response.
  • the observed effect is quite different from other known electromechanical responses. It cannot be piezoelectric because Ce 0.8 Gd 0.2 O 1.9 has a fluorite centrosymmetric structure, which is incompatible with the existence of piezoelectricity.
  • the response cannot be electrostrictive because of the argument given herein above.
  • the observed effect cannot be attributed to the movement of the oxygen vacancies, the so called chemical stress effect because such an effect requires movement of oxygen vacancies over a distance of 500 nm over the time period of 10 min (see Fig. 5 last step).
  • the voltage-stress behavior was studied on a number of samples connected in the single-clamped uniform beam mode (as presented in Figure 2 and described in Example 1) to the reflected laser-beam experiment setup.
  • the single-clamped uniform beam causes change in the radius of curvature as a result of electromechanical response. This fact was exploited for monitoring the electromechanical response by measuring the reflection from the sample of the laser beam.
  • the diode-pumped solid-state laser [by CrystaLaser®, 532nm, beam divergence of 0.5mrad] was used for these experiments.
  • Monitoring the development of electromechanical stress was done by recording the reflected laser beam with Apogee® Alta® U2000 monochrome CCD camera. The change of the reflected spot on CCD camera was translated directly into the change in stress inside the thin CGO film using geometrical parameters of the system and Stoney formula.
  • the alternating voltage was applied in a form of V AC ⁇ cos(2 ⁇ ft ) + V DC and the electromechanical fluctuations of the sample were recorded on CCD camera, as a motion of the reflected laser beam position.
  • each 2 nd (second) electromechanical peak has a higher amplitude, which is a result of both V AC and V DC , while the smaller electromechanical peaks, refer to V AC only.
  • the electromechanical response has two harmonic components relative to the applied frequency f , when the first is a function of both V AC and V DC , and the second (doubled) - of the V AC only. This explains the voltage dependence of the electromechanical response frequency.
  • the electromechanical response measured by the CCD camera was translated to the electromechanical stress inside the CGO film.
  • l the place on the sample, where the laser beam reflects from, measured from the clamped side.
  • ⁇ Y s 1 ⁇ v s t s 2 6 t f ⁇ k
  • Y s and v s are Young modulus ( ⁇ 69 GPa) and Poisson's ratio (0.2) of the substrate (glass)
  • t s and t f are the thicknesses of the substrate and film (CGO) respectively.
  • ⁇ ⁇ was calculated by averaging more than 20 values of ⁇ X .
  • the error bars were taken into account including uncertainty in all the experimental parameters.
  • Figures 8, 9 and 10 present the electromechanical stress amplitude as a function of one bias component, when the rest parameters are fixed.
  • the results presented in Figures 8, 9 and 10 fit the Eq. 1.
  • V DC 0
  • the electromechanical stress grew linearly with V DC or V AC and the dominant frequency of the response was the same as of the applied bias.
  • the deflection from linearity at high biases in Figures 8 and 9 can be explained by field saturation.
  • Figure 11 demonstrates that the CGO thin film generates mechanical force up to 1.5 mN, following the applied bias.
  • Example 1 and Figure 2 The effect of temperature on the electromechanical stress of CGO was studied on a sample in the single-clamped uniform beam mode as presented in Example 1 and Figure 2 , which was inserted to a home-made mini-furnace equipped with Eurotherm® 2216L temperature controller, closed from the five sides, to allow free fluctuations, and with a hole for the laser beam from above.
  • the sample fluctuated according to the applied bias during poling.
  • the stress amplitude increased linearly during ⁇ 18 hr of poling untill saturation of ⁇ 20MPa.
  • the above sample presented a single-clamped uniform beam electromechanical resonator, which fluctuated according to applied bias frequency.
  • the resonator demonstrated a highly efficient electromechanical transducer or, alternatively, CGO is a highly efficient electromechanical material in the given frequency and experimental setup.
  • the Electromechanical response was high at lower frequencies and decreased at higher frequency, where the electromechanical material, CGO, ceased to follow the alternating field.
  • the results for frequency behavior of the sample in double-clamped beam mode are shown in Figure 18 .
  • the sample provided two definite, separated relaxations when no mechanical resonance was applied: (i) in 0.1-1 Hz region and (ii) 10-1000 Hz region.
  • the properties of the CGO of this invention were comparable with high-end commercial electromechanically active materials.
  • CGO operated at higher fields had higher mechanical properties, and demonstrated higher stress measurements of about 36 MPa at 40 kV/cm during the experiments.

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Claims (11)

  1. Ein elektromechanischer Aktuator, der ein Cerdioxid-basiertes Material aufweist, wobei dieses Cerdioxid-basierte Material mit einem Metallion dotiert und durch die Formel CexMyO(2-δ) repräsentiert ist, wobei M ein Metallion mit einer Valenz von weniger als oder gleich vier ist, wobei 0<x<1, 0<y<1 und 0<δ<1 ist, wobei das besagte Cerdioxid-basierte Material eine Fluorit-ähnliche Struktur und Sauerstoffvakanzen aufweist, und wobei bei Anwendung eines elektrischen Feldes das Cerdioxid-basierte Material eine Verschiebung, Spannung oder eine Kombination daraus erzeugt.
  2. Ein elektromechanischer Sensor, der ein Cerdioxid-basiertes Material aufweist, wobei dieses Cerdioxid-basierte Material mit einem Metallion dotiert und durch die Formel CexMyO(2-δ) repräsentiert ist, wobei M ein Metallion mit einer Valenz von weniger als oder gleich vier ist, wobei 0<x<1, 0<y<1 und 0<δ<1 ist, wobei das besagte Cerdioxid-basierte Material eine Fluorit-ähnliche Struktur und Sauerstoffvakanzen aufweist, und wobei bei Anwendung eines elektrischen Feldes das Cerdioxid-basierte Material eine Verschiebung, Spannung oder eine Kombination daraus erzeugt.
  3. Der Aktuator oder Sensor nach Anspruch 1 oder 2, wobei das besagte Cerdioxid-basierte Material mit einem Lanthanid dotiert ist.
  4. Der Aktuator oder Sensor nach Anspruch 3, wobei das besagte Cerdioxid-basierte Material CexGdyOz ist, wobei x im Bereich zwischen 0,95-0,63, y zwischen 0,05-0,37 und z zwischen 1,815-1,975 liegt.
  5. Der Aktuator oder Sensor nach Anspruch 4, wobei das besagte CexGdyOz Ce0.8Gd0.2O1.9 ist.
  6. Ein elektromechanisches Gerät, das ein Cerdioxid-basiertes Material der Formel Ce0.8Gd0.2O1.9 aufweist, wobei dieses Cerdioxid-basierte Material eine Fluorit-ähnliche Struktur und Sauerstoffvakanzen aufweist, und wobei bei Anwendung eines elektrischen Feldes das Cerdioxid-basierte Material eine Verschiebung, Spannung oder eine Kombination daraus erzeugt.
  7. Der Aktuator, Sensor oder das Gerät nach Anspruch 1-6, wobei das besagte Cerdioxid-basierte Material dehnungsfrei ist oder die Dehnung auf gleicher Ebene des besagten Cerdioxid-basierten Materials im Bereich zwischen 0,1%-0,4% liegt.
  8. Der Aktuator, Sensor oder das Gerät nach einem der Ansprüche 1-6, wobei die besagte Verschiebung mindestens 100 pm/V beträgt.
  9. Der Aktuator, Sensor oder das Gerät nach einem der Ansprüche 1-6, wobei die besagte Spannung, die sich in dem Cerdioxid-basierten Material entwickelt, mindestens 100 MPa beträgt.
  10. Der Aktuator, Sensor oder das Gerät nach einem der Ansprüche 1-6, der/das darüber hinaus leitfähige Kontakte aufweist, wobei diese leitfähigen Kontakte Cr, Al, Ag, Ti oder eine Kombination daraus umfassen.
  11. Der Aktuator, Sensor oder das Gerät nach einem der Ansprüche 1-6, der/das von einem Substrat unterstützt wird.
EP11788584.8A 2010-10-05 2011-10-05 Elektromechanische wirkung bei metalloxiden Not-in-force EP2625729B1 (de)

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